Lea Haas¹, Peter Mlkvik^1*, Nicola A. Spaldin¹, Claude Ederer¹

1 Materials Theory, Department of Materials, ETH Zürich, Switzerland

* Corresponding authors emails: peter.mlkvik@mat.ethz.ch

DOI10.24435/materialscloud:2k-pr [version v1]

Publication date: Oct 31, 2024

How to cite this record

Lea Haas, Peter Mlkvik, Nicola A. Spaldin, Claude Ederer, Incorporating static intersite correlation effects in vanadium dioxide through DFT+V, Materials Cloud Archive 2024.177 (2024), https://doi.org/10.24435/materialscloud:2k-pr

Description

We analyze the effects on the structural and electronic properties of vanadium dioxide (VO₂) of adding an empirical inter-atomic potential within the density-functional theory+V (DFT+V) framework. We use the DFT+V machinery founded on the extended Hubbard model to apply an empirical self-energy correction between nearest-neighbor vanadium atoms in both rutile and monoclinic phases, and for a set of structures interpolating between these two cases. We observe that imposing an explicit intersite interaction V along the vanadium-vanadium chains enhances the characteristic bonding-antibonding splitting of the relevant bands in the monoclinic phase, thus favoring electronic dimerization and the formation of a band gap. We then explore the effect of V on the structural properties and the relative energies of the two phases, finding an insulating global energy minimum for the monoclinic phase, consistent with experimental observations. With increasing V, this minimum becomes deeper relative to the rutile structure, and the transition from the metallic to the insulating state becomes sharper. We also analyze the effect of applying the +V correction either to all or only to selected vanadium-vanadium pairs, and both in the monoclinic as well as in the metallic rutile phase. Our results suggest that DFT+V can indeed serve as a computationally inexpensive unbiased way of modeling VO₂ which is well suited for studies that, e.g., require large system sizes.

Materials Cloud sections using this data

Files

File name	Size	Description
dftv-data.zip MD5md5:0507add25478aed3e1d9cb2bc4340d9c	978.1 KiB	compressed archive with all QE inputs
README.txt MD5md5:ecf0a07388087719753a89a56cd92d1a	2.4 KiB	README

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External references

Keywords

DFT DFT+U+V VO2